Anthraquinone acid dyestuffs



Patented Mar. 7, 1950 V, UNITED STAT Curt G. Vog't,

" Aniline & Film Corp 2 Claims. (Cl. 260--374) Y The present inventionrelates to new compounds of the anthraquinone series, more particularlyto new acid wool dyestuffs capable of dyeing in greenish-blue shades.

The new compounds have the general formula:

ii I

S O 3MB 0 NH-R wherein Me is hydrogen, an alkali metal or ammonium and Ris fluorenyl or substituted fluorenyl wherein the substituents are inone or both of the benz nuclei and may be halogen, e. g., chlorine,bromine, etc., alkyl, e. g., methyl, ethyl, propyl, butyl, etc., alkoxy,e. g., methoxy, ethoxy, propoxy, butoxy, etc., and aralkyl, e. g..benzyl, phenylethyl, etc. These substituents being in the benz nucleiare designated herein as ar-substituents.

For the preparation of the new dyestuffs a 1-amino-4-halogen-anthraquinone-2-sulfonic acid or a salt thereof iscondensed with the corresponding fluorenamine, unsubstituted orar-substituted as aforedefined. Fluorenamines which may be so employedare. for example, 2. 3 and 9- aminofluorene, '7 chloro 2 aminofiuorene,7- bromo-2-arninofluorene, 2-bromo-7-aminofluorene.3,7-dibromo-2-aminofiuorene, '7-methyl-2- aminofluorene,'7-isobutyl-2-aminofluorene. 2- methoxy-3-aminofluorene,7-benzyl-2-aminofluorene, etc.

The condensation reaction for the preparation of the dyestuffs iscarried out by heating an aqueous solution of the1-amino-4-halogen-anthraquinone-Z-sulfonic acid or of a salt thereof inadmixture with a solution of the fluorenylamine in a water-miscibleorganic solvent such as ethanol in the presence of a catalyst for thecondensation such as copper or a copper salt and an acid binding agentsuch as sodium or potassium bicarbonate. To insure obtaining the productin the highest state of purity, the reaction is preferably carried outwith exclusion of air from the hot reaction mixture. This may beaccomplished by conducting the reaction in'an atmosphere of an inert gassuch as nitrogen or carbon dioxide or the like.

as PATENT OFFICE ANTHRAQUI'NONE ACID DYESTUFF I Union, N. J., assignorto General oration, New York, N. Y... a corporation of Delaware v NoDrawing. Application December 12, 1946,

- Serial No."715,627..

present invention are capable The dyestuffs contain but one sulfo groupand as the free acid or as the alkali metal or ammonium salt arecompounds of very limited solubility in water. They may be applied tothe dyeing of animal or nylon (linear superpolyamide) fibers in the formof aqueous dispersions prepared from the compounds previously dispersedin a suitable medium such as lignin sodium sulfonate. Thus applied, thecompounds dye wool or nylon from acid or neutral bath in greenishblueshades of good iastness to light, washing and crocking. the e fastnessproperties being the stronger in the nylon dyeings.

In view of the fact that the dyestuffs of the of dyeing animal and nylonfibers from neutral bath they are valuable in the union dyeing oftextiles, for example, in the dyeing of mixed fibers of wool and cottonor nylon and cotton. the wool and nylon in each case being dyed agreenish-blue shade whereas the cotton, which remains undyed, is nottendered as would occur where an acid solution is employed.

The invention is further illustrated by the following example to which,however, it is not intended that it be limited. Parts are by weight.

Example eter and reflux condenser. To this mixture is slowly added asolution of 135 parts of 2-fiuor-,

enamine in 144 parts of warm ethanol. The mixture is heated, withstirring, to reflux and maintained at this temperature for 3 hours. Atthis time, a sample of the mixture viewed through the microscope showsvery fine greenish-blue crystals. The reaction mixture'is parts of"low-power of a concentrated by distillation. After '70 distillateare-removed, the residue is cooled and filtered. The precipitate isadded to 800 parts of water at C. with stirring, then 30 parts of 10%hydrochloric acid is added. The solids are recovered by*ijltration. Thesludging process- 1 may be rep dystufi aite ryirig, amounts to 23 parts.

parts water is placed in a] reaction vessel equipped with a stirrer,thermor n'-' desired. The precipitated The dyestuf 'was admixed withlignin sodium sulfonate, kneaded to dryness in a Werner-Pflei- 2. Anaminoanthraquinone compound of the derer mill and the resultant powderdispersed in general formu1a:

Water. The dispersed product dyes wool and NH:

nylon from a neutral or acid aqueous bath in H beautiful greenish-blueshades, the fastness to 5 some light, washing and crocking of the dyeingon wool being good and on nylon very good.

I claim: on,

1. An aminoanthraquinone compound of the c) NH- general formula:

O NH:

" I wherein Me is a member selected from the group some consisting ofhydrogen, alkali metal and ammomum.

CURT G. VOGT. REFERENCES CITED v e .The following references are ofrecord in the wherein R is a member selected from the group file of t atconsisting of fiuorenyl and ar-halogen, 'ar-alkyl, ar-alkoxy andar-aralkyl fiuorenyl, and Me is- FOREIGN PATENTS selected from the groupconsisting of hydrogen, Number Country Date alkali metal and ammonium.568,567 Germany Jan.v 20, 1933

1. AN AMINOANTHRAQUINONE COMPOUND OF THE GENERAL FORMULA: